A green and scalable strategy has been developed for the synthesis of lignin-derived Zn single atom/N-codoped porous carbon(LCN@Zn-SAC)containing similar ZnNx sites with carbonic anhydrases.This catalyst exhibits supe...A green and scalable strategy has been developed for the synthesis of lignin-derived Zn single atom/N-codoped porous carbon(LCN@Zn-SAC)containing similar ZnNx sites with carbonic anhydrases.This catalyst exhibits superior activity on theα-alkylation of ketones with alcohols via borrowing hydrogen strategy(TON up to 15 h^(−1))than most of previously reported works.The dehydrogenation of benzyl alcohol is the rate-determining step based on kinetic experiment results.According to experimental and theoretical calculation results,Zn electron density is inversely proportional to reaction energy barriers,because Zn sites with less positive charge(ZnN_(4) and ZnN_(3)C)in Zn-SACs display better borrowing hydrogen ability than other Zn sites.Furthermore,this catalyst can be recycled by simple centrifugation,which can be reused at least 8 runs with no obvious lose in activity.To the best of our knowledge,this is the first example of non-noble metal-SAC-catalyzedα-alkylation via borrowing hydrogen strategy.展开更多
A ruthenium based catalytic system([Ru(p-cymene)Cl2]2/XantPhos with substoichiometric Cs2CO3)has been established to effectively achieve the first direct amination cyclization of 1,2,4-butanetriol with primary aromati...A ruthenium based catalytic system([Ru(p-cymene)Cl2]2/XantPhos with substoichiometric Cs2CO3)has been established to effectively achieve the first direct amination cyclization of 1,2,4-butanetriol with primary aromatic amines.The product of this sustainable hydrogen autotransfer process is valuable Naryl-3-pyrrolidinol.展开更多
A general and high-efficiency C-alkylation of oxindoles and barbituric acids has been developed by a Cp*Ir complex[Cp*Ir(2,20-bpyO)(OH)]Na with a bipyridine-based functional ligand.In particular,H_(2)O was selected as...A general and high-efficiency C-alkylation of oxindoles and barbituric acids has been developed by a Cp*Ir complex[Cp*Ir(2,20-bpyO)(OH)]Na with a bipyridine-based functional ligand.In particular,H_(2)O was selected as the solvent instead of the organic solvent in this catalytic system.Through mild reaction conditions gave a variety of corresponding alkylated heterocyclic compounds with good to excellent yields.More importantly,the gramscale C-alkylation reaction was successfully carried out with good yield using a common route with only a single purification by column chromatography.展开更多
Earth abundant metals are much less expensive,promising,valuable metals and could be served as catalysts for the borrowing hydrogen reaction,dehydrogenation and heterocycles synthesis,instead of noble metals.The unifo...Earth abundant metals are much less expensive,promising,valuable metals and could be served as catalysts for the borrowing hydrogen reaction,dehydrogenation and heterocycles synthesis,instead of noble metals.The uniformly dispersed zinc composites were designed,synthesized and carefully characterized by means of XPS,EDS,TEM and XRD.The resulting zinc composite showed good catalytic activity for the N-alkylation of amines with amines,ketones with alcohols in water under base-free conditions,while unsaturated carbonyl compounds could also be synthesized by tuning the reaction conditions.Importantly,it was the first time to realize the synthesis of 2-aryl-1H-benzo[d]imidazole derivatives by using this zinc composite under green conditions.Meanwhile,this zinc catalyst could be easily recovered and reused for at least five times.展开更多
基金the Fundamental Research Funds for the Central Universities(No.30920021120)the National Natural Science Foundation of China(Nos.32001266,21776138,and 22078161)for financial support.
文摘A green and scalable strategy has been developed for the synthesis of lignin-derived Zn single atom/N-codoped porous carbon(LCN@Zn-SAC)containing similar ZnNx sites with carbonic anhydrases.This catalyst exhibits superior activity on theα-alkylation of ketones with alcohols via borrowing hydrogen strategy(TON up to 15 h^(−1))than most of previously reported works.The dehydrogenation of benzyl alcohol is the rate-determining step based on kinetic experiment results.According to experimental and theoretical calculation results,Zn electron density is inversely proportional to reaction energy barriers,because Zn sites with less positive charge(ZnN_(4) and ZnN_(3)C)in Zn-SACs display better borrowing hydrogen ability than other Zn sites.Furthermore,this catalyst can be recycled by simple centrifugation,which can be reused at least 8 runs with no obvious lose in activity.To the best of our knowledge,this is the first example of non-noble metal-SAC-catalyzedα-alkylation via borrowing hydrogen strategy.
基金the National Natural Science Foundation of China (No. 21672027)QingLan Project of Jiangsu Province (2016)+1 种基金SixTalent-Peaks Program of Jiangsu (2016) for financial supportsupported by High-Level Entrepreneurial Talent Team of Jiangsu Province (No.2017-37)
文摘A ruthenium based catalytic system([Ru(p-cymene)Cl2]2/XantPhos with substoichiometric Cs2CO3)has been established to effectively achieve the first direct amination cyclization of 1,2,4-butanetriol with primary aromatic amines.The product of this sustainable hydrogen autotransfer process is valuable Naryl-3-pyrrolidinol.
基金support from the National Natural Science Foundation of China(No.22005179)the Natural Science Foundation of Shandong Province(Nos.ZR2020QB113,ZR2020MB018 and ZR2021QB049).
文摘A general and high-efficiency C-alkylation of oxindoles and barbituric acids has been developed by a Cp*Ir complex[Cp*Ir(2,20-bpyO)(OH)]Na with a bipyridine-based functional ligand.In particular,H_(2)O was selected as the solvent instead of the organic solvent in this catalytic system.Through mild reaction conditions gave a variety of corresponding alkylated heterocyclic compounds with good to excellent yields.More importantly,the gramscale C-alkylation reaction was successfully carried out with good yield using a common route with only a single purification by column chromatography.
基金financial support of this work by the National Natural Science Foundation of China(Nos.21776111,21861039)State Key Laboratory of Pulp and Paper Engineering(No.202001)Central Laboratory,School of Chemical and Material Engineering,Jiangnan University。
文摘Earth abundant metals are much less expensive,promising,valuable metals and could be served as catalysts for the borrowing hydrogen reaction,dehydrogenation and heterocycles synthesis,instead of noble metals.The uniformly dispersed zinc composites were designed,synthesized and carefully characterized by means of XPS,EDS,TEM and XRD.The resulting zinc composite showed good catalytic activity for the N-alkylation of amines with amines,ketones with alcohols in water under base-free conditions,while unsaturated carbonyl compounds could also be synthesized by tuning the reaction conditions.Importantly,it was the first time to realize the synthesis of 2-aryl-1H-benzo[d]imidazole derivatives by using this zinc composite under green conditions.Meanwhile,this zinc catalyst could be easily recovered and reused for at least five times.
